CN103816927B - A kind of catalyst for the synthesis of Ethylenimine, preparation method and application - Google Patents

A kind of catalyst for the synthesis of Ethylenimine, preparation method and application Download PDF

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CN103816927B
CN103816927B CN201310698874.4A CN201310698874A CN103816927B CN 103816927 B CN103816927 B CN 103816927B CN 201310698874 A CN201310698874 A CN 201310698874A CN 103816927 B CN103816927 B CN 103816927B
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catalyst
ion
carrier
ethylenimine
salt
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CN103816927A (en
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杨建明
吕剑
梅苏宁
余秦伟
惠丰
李亚妮
赵锋伟
王为强
王伟
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Xian Modern Chemistry Research Institute
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Priority to US15/105,499 priority patent/US9920008B2/en
Priority to PCT/CN2014/086008 priority patent/WO2015090084A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/182—Phosphorus; Compounds thereof with silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B01J35/19—
    • B01J35/613—
    • B01J35/633—
    • B01J35/647—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0217—Pretreatment of the substrate before coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/22—Halogenating
    • B01J37/26—Fluorinating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The present invention relates to for the synthesis of the catalyst of Ethylenimine, preparation method and application.Involved catalyst comprises carrier and the metal ion of load on carrier, and described carrier is the composite oxides of titaniferous, silicon and P elements; Described metal ion is magnesium ion, iron ion and cesium ion, and the mol ratio of magnesium ion, iron ion, cesium ion is: 1 ~ 10:1:0.1, and the quality of all metal ions is 0.5% ~ 10% of carrier quality.Involved preparation method is that roasting obtains catalyst by catalyst precursor at 350 DEG C ~ 650 DEG C, and described catalyst precursor is the mixture of the soluble-salt of carrier, the soluble-salt of magnesium, the soluble-salt of iron and caesium.Present invention also offers above-mentioned catalyst for taking amino alcohol as the application in Material synthesis Ethylenimine.Catalyst of the present invention, significantly reduces reaction temperature with General Requirements temperature higher than reduction compared with 400 DEG C.Obtained catalyst can catalytic amino alcohol molecule inner dewatering reaction, and has preferably selective.

Description

A kind of catalyst for the synthesis of Ethylenimine, preparation method and application
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of synthesize Ethylenimine catalyst, preparation method and application.
Background technology
Ethylenimine, also known as aziridine, is a kind of important fine chemical product, has purposes widely in fields such as medicine, agricultural chemicals, high-energy fuel, bonding agents.
The initial industrial making method of Ethylenimine is liquid phase method, and take MEA as raw material, the employing concentrated sulfuric acid is dehydrating agent, needs to add concentrated base in reaction, and cost is higher and produce useless inorganic salts by-product, causes serious environmental pollution.
US4301036 discloses the catalyst of tungsten oxide and Si oxide composition, and the application in synthesis Ethylenimine.
Disclose use niobium/tantalum pentoxide and alkaline-earth metal and (or) iron/chromated oxide in US4488591 and synthesize the method for Ethylenimine as catalyst.
The composite oxide catalysts that US433717 discloses one Nb or Ta oxide and alkaline earth oxide (BaO) produces the method for Ethylenimine.First the chloride of Nb or Ta is made load impregnating solution useful, be carried on carrier (0.1m 2/ g ~ 1.0m 2/ g) surface, through 450 ~ 550 DEG C of calcination process 2 ~ 4h, obtained catalyst.Reaction temperature 400 DEG C, monoethanolamine conversion ratio 13.87 (mol) %, Ethylenimine selective 82.09 (mol) %, and have a small amount of acetaldehyde, ethamine, pyrazine and alkyl pyrazine to generate.
CN2007100109625 discloses a kind of catalyst for the synthesis of Ethylenimine compounds.This catalyst consists of: X ay bo c(HZSM-5) d, wherein X is selected from alkali metal, and Y is selected from phosphorus or boron element, and O is oxygen element, and a, b, c, d are the mol ratios of X, Y, O, ZSM-5 zeolite, and as d=1, a=0.01 ~ 0.1, b=0.001 ~ 0.1, c value depends on a, b.Reaction temperature 420 DEG C, monoethanolamine conversion ratio 84 (mol) %, Ethylenimine selective 84 (mol) %.
Ethylenimine specific surface area of catalyst and Acid-Base strengths and catalyst activity, selective closely related.When general specific area is larger, the catalyst of load just has higher catalytic activity, and the preparation of such catalyst need through high temperature (>=600 DEG C) calcination steps, due to the localized hyperthermia that very exothermic reaction is formed, after making sintering of catalyst, specific area significantly reduces, and causes catalyst activity and selectivity to reduce.Consider the economic factors in industrial process, usually pursue catalyst more high selectivity and more the long-life more important than materials conversion rate, with ensure material conversion become as much as possible needed for target product and reduce the generation of unnecessary accessory substance.
In prior art, the molecule inner dewatering reaction of amino alcohol is under lower temperature (~ 370 DEG C), catalyst activity and selectivity is lower, reaction temperature is high, General Requirements temperature could be carried out quickly higher than 400 DEG C of reactions, but the generation of deaminizating and intermolecular condensation reaction easily occurs and accessory substance is increased, and causes the selective reduction of Ethylenimine, general weight selectivities is lower than 65%, and service life is short.
Summary of the invention
For defect or the deficiency of prior art, an object of the present invention is to provide that a kind of specific area is large, pore volume is large, low temperature active is high, the catalyst for the synthesis of Ethylenimine of long service life.
For this reason, catalyst provided by the invention comprises carrier and the metal ion of load on carrier, and described carrier is the composite oxides of titaniferous, silicon and P elements; Described metal ion is magnesium ion, iron ion and cesium ion, and the mol ratio of magnesium ion, iron ion, cesium ion is: 1 ~ 10:1:0.1, and the quality of all metal ions is 0.5% ~ 10% of carrier quality.
Another object of the present invention is to provide the preparation method of above-mentioned carrier and the preparation method of catalyst.
For this reason, the preparation method of the carrier provided described in comprises:
(1) by silica, titanium dioxide, ammonium phosphate salt mixing, SiO is counted in the form of an oxide 2: TiO 2: P 2o 5weight ratio is 5 ~ 20:80:15 ~ 5, then adds binding agent, mediates, and extrusion is shaped, dry, 600 ~ 900 DEG C of roastings, the composite oxides of obtained titaniferous, silicon and P elements;
Described ammonium phosphate salt is ammonium phosphate, diammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP);
Described binding agent is Ludox or boehmite;
(2) under anaerobic, 100 DEG C ~ 200 DEG C conditions, step (1) gained composite oxides and hydrogen fluoride carry out fluorination reaction and obtain catalyst carrier.
Preferably, the consumption of described binding agent is 10% ~ 30% of the quality of titanium dioxide.
The preparation method of the catalyst provided comprises:
By catalyst precursor at 350 DEG C ~ 650 DEG C, roasting obtains catalyst, and described catalyst precursor is the mixture of the soluble-salt of carrier, the soluble-salt of magnesium, the soluble-salt of iron and caesium.
For prior art defect or deficiency, present invention also offers above-mentioned catalyst for taking amino alcohol as the application in Material synthesis Ethylenimine.
Preferably, under above-mentioned catalyst existence condition, when taking amino alcohol as Material synthesis Ethylenimine, reaction temperature is 370 DEG C ~ 385 DEG C.
Compared with prior art, beneficial effect of the present invention is:
(1) synthesis Ethylenimine catalyst of the present invention, adopts at 100 DEG C ~ 200 DEG C temperature, selects SiO 2as pore creating material, utilize the SiO in carrier 2chain structure and easily react with HF the feature forming volatile fluorinated silicon compound, will flow down continuous pore passage structure after being fluorinated removing, thus increase specific area and pore volume, prepare and there is high specific area and the catalyst of large pore volume, specific area>=40m 2/ g, pore volume>=0.20mL/g, average pore size≤9nm, improve reaction raw materials and the diffusion effect of product in catalyst pores.
(2) synthesis Ethylenimine catalyst of the present invention, significantly reduces reaction temperature with General Requirements temperature higher than reduction compared with 400 DEG C.Obtained catalyst can catalytic amino alcohol molecule inner dewatering reaction, and has best selective, and 370 DEG C time, MEA conversion ratio can reach 38%, and Ethylenimine is selective reaches 95%.
(3) catalyst long service life of the present invention, active basic maintenance is stablized, and in 1000h, MEA conversion ratio can reach 32%, and Ethylenimine is selective reaches 96%.
(4) catalyst of the present invention can be used in multiple amino alcohol molecule inner dewatering reaction.
Detailed description of the invention
In order to realize above-mentioned task, the present invention takes following technical solution: adopt at 100 DEG C ~ 200 DEG C temperature, select SiO 2as pore creating material, utilize the SiO in carrier 2chain structure and easily react with HF the feature forming volatile fluorinated silicon compound, will flow down continuous pore passage structure after being fluorinated removing, thus increase specific area and pore volume, there is high specific area and large pore volume.Again through the impregnated activated component of impregnation steps, obtained catalyst.
The consumption of binding agent of the present invention can be determined according to the mixture in step (1) in extrusion shaping.Wherein Ludox used is silica quality percentage composition is the aqueous solution of 20% ~ 30%.
The soluble-salt preferably nitrate of magnesium used in the present invention or chloride, the soluble-salt preferably nitrate of iron or chloride, the soluble-salt preferably nitrate of caesium or chloride.
Synthesis Ethylenimine catalyst prepared by the present invention, its activity rating device can carry out in common fixed-bed tube reactor, and reactor size is catalyst packing is entered reactor, is heated to reaction temperature, by measuring pump charging, sample analysis after reaction, analytical instrument is GC-930 gas chromatograph.
Monoethanolamine conversion ratio of the present invention, Ethylenimine is selective is defined as follows:
Monoethanolamine conversion ratio C mEA, the chromatogram area percent of monoethanolamine in %=1-product liquid
In selectivity of product S, %=product liquid ethyleneamines chromatogram area percent/product liquid in deduct the chromatogram area percent of monoethanolamine
The present invention synthesizes the catalyst of Ethylenimine, comprises in the molecule inner dewatering reaction for other amino alcohol, and amino alcohol is the alkamine compound with ortho position structure, and its structure is:
R 1for hydrogen, methyl, ethyl or methylol, R 2for hydrogen, methyl, ethyl or methylol, A is hydroxyl or amino, and B is hydroxyl or amino, and is hydroxyl or amino when A with B is different; Wherein amino alcohol is monoethanolamine, isopropanolamine, 3-amino-1,2-PD, 2-amino-2-methyl-1-propanol, also can be other amino butanol, aminopentanol.Preferred 3-amino-1,2-PD, 2-amino-2-methyl-1-propanol.
Be below the embodiment that inventor provides, these embodiments are preferably examples, are mainly used in explaining and understanding technical scheme of the present invention further, the invention is not restricted to these embodiments.
Embodiment 1:
According to oxide basis SiO 2: TiO 2: P 2o 5weight ratio is the configuration of 5:80:15 stoichiometric proportion.
By white carbon 10g, titanium dioxide 160g, after diammonium hydrogen phosphate 55.7g mixes, then add Ludox, Ludox addition is 20% of the quality of titanium dioxide, mediate, extrusion is shaped, 120 DEG C of dry 6h, 350 DEG C of roasting 6h in Muffle furnace, at 1 DEG C/min temperature programming to 650 DEG C roasting 6h, the composite oxides of obtained titanium, silicon, phosphorus composition.
Load tubular reactor by after the composite oxides cooling of titanium, silicon, phosphorus composition, being warming up to 150 DEG C, is then HF:N by volume ratio 2the mixture of=1:5 fluoridizes 2h, obtains catalyst carrier.This carrier low-temperature nitrogen adsorption method measures its specific area 42m 2/ g, pore volume 0.22mL/g, average pore size 5.6nm.
Be 10:1:0.1 load according to the mol ratio of magnesium ion, iron ion, cesium ion, get magnesium nitrate 29.6g, ferric nitrate 4.84g, cesium nitrate 0.4g is configured to solution, by the impregnation of catalyst carriers 8h obtained, dry after taking out, at 450 DEG C, obtain catalyst with air roasting.
Above-mentioned Catalyst packing is entered reactor, loadings 30mL, is heated to reaction temperature 370 DEG C, nitrogen as protective gas, nitrogen and MEA gas volume than 16, in the total air speed of standard state gas: 3600h -1, react and carry out under normal pressure or vacuum condition, after reaction 8h, sample analysis after reacting gas water absorbs, MEA conversion ratio 38%, Ethylenimine selective 95%, after reaction 1000h, MEA conversion ratio 32%, Ethylenimine selective 96%.
Embodiment 2:
Embodiment 2 is substantially identical with preparation process in embodiment 1, unlike according to SiO 2: TiO 2: P 2o 5weight ratio is the configuration of 10:80:10 stoichiometric proportion.Catalyst carrier low-temperature nitrogen adsorption method measures its specific area 43.2m 2/ g, pore volume 0.21mL/g, average pore size 5.8nm.
According to 5.3% load that metal ion is carrier quality, the mol ratio of magnesium ion, iron ion, cesium ion is 8:1:0.1, and configuration soluble metal salt solution, by the impregnation of catalyst carriers 8h obtained, dry after taking out, at 350 DEG C, in nitrogen, roasting obtains catalyst.
Above-mentioned Catalyst packing is entered reactor, loadings 30mL, is heated to reaction temperature 380 DEG C, nitrogen as protective gas, nitrogen and MEA gas volume than 16, in the total air speed of standard state gas: 3000h -1, react and carry out under normal pressure or vacuum condition, after reaction 8h, sample analysis after reacting gas water absorbs, MEA conversion ratio 68%, Ethylenimine selective 96%, after reaction 1000h, MEA conversion ratio 56%, Ethylenimine selective 94%.
Embodiment 3:
Embodiment 2 is substantially identical with preparation process in embodiment 1, unlike according to SiO 2: TiO 2: P 2o 5weight ratio is the configuration of 15:80:5 stoichiometric proportion.Catalyst carrier low-temperature nitrogen adsorption method measures its specific area 46.8m 2/ g, pore volume 0.25mL/g, average pore size 6.1nm.
According to 0.5% load that metal ion is carrier quality, the mol ratio of magnesium ion, iron ion, cesium ion is 1:1:0.1, and configuration soluble metal salt solution, by the impregnation of catalyst carriers 8h obtained, dry after taking out, at 650 DEG C, obtain catalyst with air roasting.
Above-mentioned Catalyst packing is entered reactor, loadings 30mL, is heated to reaction temperature 380 DEG C, nitrogen as protective gas, nitrogen and MEA gas volume than 16, in the total air speed of standard state gas: 3200h -1, react and carry out under normal pressure or vacuum condition, after reaction 8h, sample analysis after reacting gas water absorbs, MEA conversion ratio 86%, Ethylenimine selective 92%.
Embodiment 4:
Embodiment 4 operates substantially the same manner as Example 1, difference is 10.0% load of carrier quality according to metal ion, the mol ratio of magnesium ion, iron ion, cesium ion is 5:1:0.1, configuration soluble metal salt solution, by the impregnation of catalyst carriers 8h obtained, dry after taking out, at 650 DEG C, obtain catalyst with air roasting.
Employing isopropanolamine is reaction raw materials, and catalytic reaction condition and analysis condition are with embodiment 1.Isopropanolamine conversion ratio 52%, 2-methyl ethylene imines selective 86%.
Embodiment 5:
Embodiment 5 operates substantially the same manner as Example 2, difference is 8.5% load of carrier quality according to metal ion, the mol ratio of magnesium ion, iron ion, cesium ion is 3:1:0.1, configuration soluble metal salt solution, by the impregnation of catalyst carriers 8h obtained, dry after taking out, at 650 DEG C, obtain catalyst with air roasting.
Adopt 3-amino-1,2-PD to be reaction raw materials, reaction temperature is 385 DEG C.Catalytic reaction condition and analysis condition are with embodiment 1.3-amino-selective 24.7%, 3-amino-epoxy propane selectivity 9.1% of selective 53.2%, the 2-methylol Ethylenimine of 1,2-PD conversion ratio 62%, 3-hydroxyl-1-azetidine, other is 13.0% years old.
Embodiment 6:
Embodiment 6 operates substantially the same manner as Example 3, and difference adopts 2-amino-2-methyl-1-propanol to be reaction raw materials, and reaction temperature is 379 DEG C.Catalytic reaction condition and analysis condition are with embodiment 1.2-amino-2-methyl-1-propanol conversion ratio 47%, 2,2-ethylene dimethyl imines selective 87.5%.

Claims (5)

1. for the synthesis of a catalyst for Ethylenimine, it is characterized in that, this catalyst comprises carrier and the metal ion of load on carrier, and described carrier is the composite oxides of titaniferous, silicon and P elements; Described metal ion is magnesium ion, iron ion and cesium ion, and the mol ratio of magnesium ion, iron ion, cesium ion is: 1 ~ 10:1:0.1, and the quality of all metal ions is 0.5% ~ 10% of carrier quality;
The preparation of described carrier comprises:
(1) by silica, titanium dioxide, ammonium phosphate salt mixing, SiO is counted in the form of an oxide 2: TiO 2: P 2o 5weight ratio is 5 ~ 20:80:15 ~ 5, then adds binding agent, mediates, and extrusion is shaped, dry, 600 ~ 900 DEG C of roastings, the composite oxides of obtained titaniferous, silicon and P elements;
Described ammonium phosphate salt is ammonium phosphate, diammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP);
Described binding agent is Ludox or boehmite;
(2) under anaerobic, 100 DEG C ~ 200 DEG C conditions, step (1) gained composite oxides and hydrogen fluoride carry out fluorination reaction and obtain catalyst carrier.
2., as claimed in claim 1 for the synthesis of the catalyst of Ethylenimine, it is characterized in that, the consumption of described binding agent is 10% ~ 30% of the quality of titanium dioxide.
3., as claimed in claim 1 for the synthesis of the catalyst of Ethylenimine, it is characterized in that, the preparation method of this catalyst comprises:
By catalyst precursor at 350 DEG C ~ 650 DEG C, roasting obtains catalyst, and described catalyst precursor is the mixture of the soluble-salt of carrier, the soluble-salt of magnesium, the soluble-salt of iron and caesium.
4. the catalyst described in the arbitrary claim of claim 1-3 is used for amino alcohol being the application in Material synthesis Ethylenimine.
5. apply as claimed in claim 4, it is characterized in that, reaction temperature is 370 DEG C ~ 385 DEG C.
CN201310698874.4A 2013-12-18 2013-12-18 A kind of catalyst for the synthesis of Ethylenimine, preparation method and application Active CN103816927B (en)

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CN201310698874.4A CN103816927B (en) 2013-12-18 2013-12-18 A kind of catalyst for the synthesis of Ethylenimine, preparation method and application
US15/105,499 US9920008B2 (en) 2013-12-18 2014-09-05 Catalyst for synthesizing ethylenimine as well as preparation method and application thereof
PCT/CN2014/086008 WO2015090084A1 (en) 2013-12-18 2014-09-05 Catalyst for synthesizing ethylenimine as well as preparation method and application thereof

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CN103816927B (en) * 2013-12-18 2015-12-30 西安近代化学研究所 A kind of catalyst for the synthesis of Ethylenimine, preparation method and application
CN104475144B (en) * 2014-11-28 2017-02-01 西安近代化学研究所 In-situ regeneration method for catalyst for intramolecular dehydration of amino alcohol compound
CN106345499B (en) * 2016-08-04 2019-10-11 盱眙恒信粘土科技有限公司 It is a kind of load P elements Attapulgite Catalyst preparation method and its reformed oil removing trace amounts of olefin in application
CN106890666B (en) * 2017-02-09 2019-06-28 西安近代化学研究所 A kind of catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3561456D1 (en) * 1984-05-21 1988-02-25 Toa Gosei Chem Ind Process for the production of acrylic acid or methacrylic acid
JPH0791239B2 (en) * 1988-11-22 1995-10-04 株式会社日本触媒 Method for producing ethylenediamine
US5262570A (en) 1988-11-22 1993-11-16 Nippon Shokubai Kagaku Kogyo Co., Ltd. Method of producing ethylenediamines
CA2010937A1 (en) * 1989-02-27 1990-08-27 Hideaki Tsuneki Method for regeneration of catalyst for producing aziridine compounds
WO1991019696A1 (en) * 1990-06-21 1991-12-26 Nippon Shokubai Co., Ltd. Process for producing n-substituted aziridine compound
US5236107A (en) 1992-09-21 1993-08-17 Stull Closure Technologies, Inc. Dispensing cap construction
US8586172B2 (en) * 2008-05-06 2013-11-19 General Electric Company Protective coating with high adhesion and articles made therewith
US8258073B2 (en) * 2010-03-23 2012-09-04 Ineos Usa Llc Process for preparing improved mixed metal oxide ammoxidation catalysts
CN102295581A (en) * 2010-06-24 2011-12-28 中国石油化工股份有限公司 Method for preparing 3,4-dichlorobenzonitrile by ammonia oxidation
CN102744090B (en) * 2011-04-20 2014-12-10 中国石油化工股份有限公司 Catalyst for ammoxidation preparation of 2,4-dichlorobenzonitrile
CN103816927B (en) * 2013-12-18 2015-12-30 西安近代化学研究所 A kind of catalyst for the synthesis of Ethylenimine, preparation method and application

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